Castable fluorocarbon binders for propellants

ABSTRACT

1. A castable binder composition comprising the following constituents: A FLUOROCARBON MONOMER SELECTED FROM THE GROUP CONSISTING OF 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate, 1H, 1H, 9Hhexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-1heptanoacrylate, 1H, 1H, 5H-octafluoro-1-pentanoacrylate and mixtures thereof; A PLASTICIZER SELECTED FROM THE GROUP CONSISTING OF TRIETHYLENE GLYCOL DINITRATE, PENTAERYTHRITOL TRINITRATE, TRIMETHYLOL ETHANE TRINITRATE, DIETHYLENE GLYCOL DINITRATE, BUTANEDIOL DINITRATE, A COPOLYMER OF VINYLIDENE FLUORIDE AND PERFLUOROPROPYLENE, BIS(2-FLUORO-2,2-DINITROETHYL) FORMAL AND MIXTURES THEREOF; A CROSS-LINKING AGENT SELECTED FROM THE GROUP CONSISTING OF TRIALLYCYANURATE AND DIVINYL BENZENE; AND A CATALYST SELECTED FROM THE GROUP CONSISTING OF AZOBISISOBUTYRONITRILE, BENZOYL PEROXIDE, DICHLOROBENZOYL PEROXIDE AND METHYLETHYLKETONE PEROXIDE.

O United States Patent 1151 3,640,785 ODrobinak et al. 1 Feb. 8, 197 2 [54] CASTABLE FLUOROCARBON BINDERS 3,493,546 2/1970 Cottrill et al ..l49/l 9 X FOR PROPELLANTS Primary Examiner-Leland A. Sebastian 1 Inventors John ovmbmaki Mart"! Kwfimn, Attorney-G. .1. Rubens, P. 11. Firsht and v. c. Muller both of China Lake, Calif. I 731 Assignee: The United States oi America as EXEMPLARY CLAIM represented by the Secretary of the Navy 1. A castable binder composition comprising the following 221 Filed: Aug. 28, 1964 mwmems: [21] Appl, No.1 394,379 a fluorocarbon monomer selected from the group consisting of 1H, 1H, 9H-hexadeeafluoro-1-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H- [52] US. Cl. ..149/88, 149/19, 149/93 dodecafluoro 1 heptanoacrylate 1H, 1H 5H Ctafluoro 1 149/109, 260/324, 260/318 F, 260/861 E, penmnoacryme and mixtures thereof;

260/873. 260/895 H [51] Int. Cl. ..C06b 3/00 a plasticizer selected from the group consisting of triethylene [58] Field of Search ...............260/89.5, 32.4, 33.8 F, 86.1 E, glycol dinitrate, pentaerythritol trinitrate, trimethylol ethane 260/873, 89.5 H; 149/19, 88, 93, 109 trinitrate, diethylene glycol dinitrate, butanediol dinitrate, a

I copolymer of vinylidene fluoride and perfluoropropylene, [56] References Cited bis( 2-fluoro-2,2-dinitroethyl) formal and mixtures thereof; UNITED STATES PATENTS a cross-linking agent selected from the group consisting of 2,31 1,501 10/1957 Stedry ..2o0/41 manycyamate and benme" and 2133915 13 6/1958 Ahlbl'echt a catalyst selected from the group consisting of a20- 310221149 2/1962 crflmer bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl 3,023,573 3/1962 Fnedman peroxide and methylethylketone peroxide. 3,235,421 2/1966 Berenbaum et a1. 3,255,059 6/1966 Hamermesh 149/19 19 Claims, N0 Drawings CASTABLE FLUOROCARBON BINDERS FOR PROPELLANTS The invention herein described may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

The present invention relates to new fluorocarbon binder compositions and to the preparation thereof.

A great need has been demonstrated in the fields of propellants, explosives and pyrotechnics for a dense binder which would be processed by casting operations. Work on metallized extruded fluorocarbon propellants has shown that propellants with high boost velocity and moderate to high specific impulses could be obtained using these nonenergetic but high-density binders. In volume limited rocket and missile systems density plays an extremely important role in determining their range. These extruded fluorocarbon propellants have done much to increase their range. The limiting factor of the extruded fluorocarbon propellants has been in obtaining large diameter grains and various shapes. The castable fluorocarbon propellants made possible by the present novel binder system overcome this limiting factor. Extruded fluorocarbon pyrotechnic materialsand isostatically pressed fluorocarbon explosives have been demonstrated to be superior to their nonfluorocarbon counterparts. However, the limiting factor of these extruded and pressed materials has been the inability to obtain various odd-shaped materials other than the simple conventional shapes, but with the castable fluorocarbon binder, this limitation factor has been eliminated. The present invention contemplates using a free-radical addition-type polymerization to form a binder which can be used directly in castable propellant, explosive, and pyrotechnic formulations.

It is therefore an object of this invention to provide a new binder for use in various propellant and explosive formulations which will enable casting of the final product into any desired shape.

Another object is to provide a binder which when used for propellant formulations will form a castable product which maintains the ballistic characteristics of extruded propellants.

Still another object is to provide a new binder material which will save time in manufacturing a finished propellant tionwill become readily apparent from the following detailed description.

The composition of the present invention for castable fluorocarbon binders comprises a fluorocarbon monomer selected from the group consisting of 1H. 1H, 9l-l-hexadecafluoro-l-monomethacrylate, 1H, ll-l, 9H-hexadecafluoro-l-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-lheptanoacrylate, 1H, 1H, SI-l-octafluoro-l-pentanoacrylate and mixtures thereof; a plasticizer selected from the group consisting of triethylene glycol dinitrat, pentaerythritol trinitrate, trimethylol ethane trinitrate, diethylene glycol dinitrate, butanediol dinitrate, a copolymer of vinylidene fluoride and perfluoropropylene (Viton) bis(2-fluoro-2,2- dinitroethyl) formal, a fluorinated polyester and mixtures thereof; a cross-linking agent selected from the group consisting of triallylcyanurate and divinyl benzene; and a catalyst selected from the group consisting of azo-bisisobutyronitrile,

benzoyl peroxide, dichlorobenzoyl peroxide, and methylethylketone peroxide.

Vinyl monomers selected from the group consisting of acrylic acid, acrylonitrile, vinylacetate, dinitropropylacrylate and styrene have also been admixed with the fluorocarbon monomers used above and the resulting binder compositions tested successfully, as shown herein. The polymerized fluorinated monomers such as Viton and fluorinated polyester influence the viscosity of the binder composition thereby permitting efficient loading of solid fuel and oxidizer ingredients of the various propellant formulations utilizing the present binder formulations.

The cross-linking agents apparently form a three-dimensional polymeric network with the fluorocarbon monomers which provide improved physical properties at the elevated temperatures at which the binder composition is to be used.

Certain wetting agents may be added as processing aids in the manufacture of the present formulation. Among those found suitable were perfluorooctanoic acid and phosphoric acid esters of fluoroalcohols.

The following are representative examples of the successful combinations utilizing a free-radical addition-type polymerization. These examples should not be considered as limiting the invention. They have been divided into groups according to test data results on elongation and density and ab breviations identified hereinafter have been used for the compounds used in the formulations.

identification of the abbreviations referred to above are as follows:

TEGDN Triethylene glycol dinitrate PETRIN Pentaerythritol trinitrale TMETN Trimethylol ethane trinitrate DEGDN Diethylene glycol dinitrate BDDN L4-butanediol dinitratc FEFO Bis(2-fluoro-2,2-dinitroethyl) formal VViton (copolymer of vinylidene fluoride and perfluoropropylene) PE Polyester FPE Fluorinated polyester C,MA 1H, 1H, 9H-hexadecafluoro-lnonanomethyacrylate C,A lH. lH. 9H-hexadecafluoro4 nonanoacrylate C,A 1H. 1H. 7H-dodecafluoro-lheptanoacrylate C,A Hi, i", SH-octafluoro-lpentanoacrylate AA Acrylic acid AN Acrylonitrile VA Vinylacetate St Styrene DNPA Dinitropropylacrylate TAC Triallylcyanurate DVB Divinyl benzene Cat. Catalyst free-radical examples, azobis-iso-butyronitrile, benzoyl peroxide, dichloro-benzoyl peroxide, methyl ethyl ketone peroxide EXAMPLE I Elongation-0 to 300% Density0.8l .50 g./cc.

Composition k by weight Sample C MA C A Cat.

l 99 l 2 89 l0 1 3 79 20 l 4 69 30 l 5 59 40 l 6 49 50 l EXAMPLE Il Elongations-from about I00 to 300% Desnityl .50-1 .80 gJcc.

Composition-k by weight EXAMPLE XII Elongationabout 250% Dens1ties-1.50-1.8O gJcc.

Composition, percent by weight Sample No. CrMA 05A V TAC Cat. 'IMEIN DE G DN' 'BDDN EXAMPLE XIII Elongation-above 250% Densities-1.50180 gJcc.

Composition. percent by weight Sample No. CQMA A V TAO Cat. PETRIN TE GDN BDDN DE GDN TME'IN 1 56 21. 9 2 O. 1

EXAMPLE XIV Elongation-about 200% Densities-1.54.80 gJcc.

EXAMPLE XV Elongation-about 250% Densities-4.504.130 gJcc.

Com position. percent by weight Sample No C MA 0511 V St TAO Cat. DEGDN TEMETN BDDN TEGDN PETRIN 1 55.9 18 1O 5 1 0.01 10 2 52. 9 16 10 5 1 O. 1 3 55. 9 18 10 5 1 0. 1 4 52. 9 16 10 5 1 0. 1 5 55. 9 18 10 5 1 0. 1 6 52. 9 16 10 5 1 O. 1 7 55. 9 18 10 5 1 0. 1 8 52. 9 16 10 5 1 0. 1 9 55. 9 18 10 5 1 0. 1 10 52. 9 16 10 5 1 0. 1

EXAMPLE XVI Elongation-about 200% Densities-1504.80 gJcc.

Composition, percent by weight OQMA. Cm V St TAO Cat. BDDN DEGDN TMETN TEGDN PETRIN 54.9 18 10 5 2 0.1 10 52.9 15 10 5 2 o. 1 54.9 18 10 5 2 0.1 52.9 15 10 5 2 0.1 54.9 18 10 5 2 0.1 52. 9 15 10 5 2 0. 1 54. 9 18 10 5 2 0. 1 52.9 15 10 5 2 o. 1 54. 9 1s 10 5 2 0. 1 52.9 15 10 5 2 0.1

The above formulations may be mixed in three ways to conwhereby the viscosity increases to about the consistency of trolthe viscosity: honey;

a. The fluorinated monomer mixture such as shown In Exb. A fluorinated polymeric plasticizer such as Viton can be ample 1, sample No. 3 is polymerized to about 5 to 20 percent dissolyed inacetone followed by the addition of one of the step necessary for removal of the acetone is eliminated. This process may take a little longer to dissolve the Viton.

fluorinated monomers such as 1,1 ,S-trihydro-octafluoro- 1 pentanoacrylate, with mixing until a homogeneous solution is obtained. The acetone is then removed by evaporation;

c. A fluorinated plasticizer such as Viton can be cut up into small pieces to create a large surface and dissolved in one of 5 the fluorinated monomers with constant mixing and/or heat. A catalyst is dissolved in the cooled solution or in the mixture to which the comonomer previously prepared has been added.

By using the fluorinated monomers instead of acetone the Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed is: 1. A castable binder composition comprising the following constituents:

a fluorocarbon monomer selected from the group consisting constituents:

Constituents Percent by weight monomethacrylate 46-62 111, 11-1, SH-octafluoro-lpentanoac ry late 1 6-23 Copolymer of vinylidene 4 fluoropropylene 10 Triallylcyanurate l-2 Azobisisobutyronitrile ODS-0.2 Triethylene glycol trinitrate 5-20 3. A castable binder composition comprising the following constituents:

Constituents Percent by weight 5. A castable binder composition comprising the following constituents:

Constituents Percent by weight .lBJ HJXl-hexadecafluoro 1 monumethacrylate 51-56 pentanoacrylate 16-22 Copolymer of vinylidene fluoride and perfluoropropylene 10 Triallylcyanurate l-2 Azo-bisisobutyronitrile 0.05-0.2 Pentaerythritol trinitrate 10-15 6. A castable binder composition comprising the following constituents:

a fluorocarbon monomer selected from the group consisting of 1H, 1H, 9l-l-hexadecafluoro-1-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-l-nonanoacrylate, 1H, 1H, 7H- dodecafluoro-l-heptanoacrylate, 1H, 1H, SH-octafluorol-pentaenoacrylate and mixtures thereof;

a vinyl monomer selected from the group consisting of acrylic acid, acrylonitrile, vinylacetate, dinitropropylacrylate, styrene'and mixtures thereof;

a plasticizer selected from the group consisting of triethylene glycol dinitrate, pentaerythritol trinitrate, trimethylol ethane trinitrate, diethylene glycol dinitrate, butanediol dinitrate, a copolymer of vinylidene fluoride and perfluoropropylene, bis(2-fluoro-2,2-dinitroethyl) formal and mixtures thereof;

a cross-linking agent selected from the group consisting of triallylcyanurate and divinyl benzene; and

a catalyst selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide.

7. A castable binder composition comprising the following constituents:

Constituents Percent by weight monomethacrylate 52-56 1H, 1H, SH-octafluoro-lpentanoacrylate 15-18 Copolymer of vinylidene fluoride and perfluoropropylene l0 Styrene 5 Triallylcyanurate 1-2 Benzoyl peroxide 0.01-0.2 Diethylene glycol dinitrate 10-15 8. The composition of claim 7 with trimethylol ethane trinitrate in lieu of diethylene glycol dinitrate.

9. The composition of claim 7 with 1,4-butanediol dinitrate in lieu of diethylene glycol dinitrate.

10. The composition of claim 7 with pentaerythritol trinitrate in lieu of diethylene glycol dinitrate.

11. The composition of claim 7 with triethylene glycol dinitrate in lieu of diethylene glycol dinitrate.

12. A fluorocarbon binder composition comprising the following constituents:

a fluorocarbon monomer selected from the group consisting of 1H, 1H, 9H-hexadecafluoro-l-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-l-nonanoacrylate, 1H, 1H, 7H- dodecafluoro-l-heptanoacrylate, 1H, 1H, 5H-octafluorol-pentanoacrylate and mixtures thereof;

a cross-linking agent selected from the group consisting of triallylcyanurate and divinyl benzene; and

a catalyst selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide, and methyl ethylketone peroxide.

Constituents Percent by weight Fluorocarbon monomer 95-99 Cross-linking agent 0.3- Catalyst 0.5-l

said fluorocarbon monomer selected from a group consisting of 1H, 1H, 9H-hexadecafluoro-l-nonanoacrylate, 1H, lH, 7l-l-dodecafluoro-l-heptanoacrylate, 1H, lH, 5Hoc- -tafluoro-l-pentanoacrylate, 1H, 1H, 9H-hexadecafluorol-nonanomethyacrylate; said cross-linking agent selected from a group consisting of triallylcyanurate and divinyl benzene; and said catalyst selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide. 16. A binder composition comprising the following constituents:

Constituents Percent by weight Fluorocarbon monomer 94-96 Vinyl monomer l-S Cross linking agent 03-4 Catalyst 0.l-l

said fluorocarbon being a member selected from a group consisting of 1H, 1H, 9H-hexadecafluorol monomethacrylate, l H, l H, 9H-hexadecafluoro- 1 nonanoacrylate, 1H, 1H, 7H-dodecafluorol -heptanoacrylate, 1H, 1H, Sl-l-octafluorol-pentanoacrylate and mixtures thereof;

said vinyl monomer being a member selected from a group consisting of acrylic acid, acrylonitrile, vinylacetate, dinitropropylacrylate and styrene;

said cross-linking agent being a member selected from the group consisting of triallylcyanurate and divinyl benzene; and said catalyst being a member selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide. 17. A binder composition comprising the following constituents:

Constituents Percent by weight monomethacrylate 65-85 pentanoacrylale l4-30 Acrylic acid l5 Triallylcyanurate 0.3-l 0.ll

Azo-hisisobutyronitrile 18. A binder composition comprising the following const tu nts;

Constituents Percent by weight monomethacrylate 65-79 l". l, SH-octafluoro-lpentanoacrylate 17-30 Acrylonitrile l.55 Triallylcyanurate 0.3-l Azo-bisisobutyronitrile 0. 1-05 19. A binder composition comprising the following constituents:

Constituents Percent by weight pentanoacrylate 20.24 Dinitropropylacrylate 5-20 Azo-bisisobutyronitrile Dal-0.3 Triallylcyanurate 0.3l 

1. A CASTABLE BINDER COMPOSITION COMPRISING THE FOLLOWING CONSTITUENTS: A FLUOROCARBON MONOMER SELECTED FROM THE GROUP CONSISTING OF 1H, 1H, 9H-HEXADEFACLUORO-1-MONOMETHACRYLATE, 1H, 1H, 9H-HERADECAFLUORO-1-NONANOCARYLATE, 1H, 1H, 7HDODECAFLUORO-1-HEPTANOCARYLATE, 1H, 1H, 5H-OCTAFLUORO-1PENTANOACRYLATE AND MIXTURES THEREOF: A PLASTICIZER SELECTED FROM THE GROUP CONSISTING OF TRIETHYLENE GLYCOL DINITRATE, PENTAERYTHRITOL TRINITRATE, TRIMETHYLOL ETHANE TRINIRATE, DIETHYLENE GLYCOL DINITRATE, BUTANEDIOL DINITRATE, A COPOLYMER OF VINYLIDENE FLUORIDE AND PERFLUOROPROPYLENE, BIX(2-FLUORO-2,2-DINITROETHYL) FORMAL AND MIXTURES THEREOF; A CROSS-LINKING AGENT SELECTED FROM THE GROUP CONSISTING OF TRIALLYCYANURATE AND DIVINYL BENZENE; AND A CATALYST SELECTED FROM THE GROUP CONSISTING OF AZOBISISOBUTYRONITRILE, BENZOYL PEROXIDE, DICHLOROBENZOYL PEROXIDE AND METHYLETHYLKETONE PEROXIDE.
 2. A castable binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 46-62 1H, 1H, 5H-octafluoro-1- pentanoacrylate 16-23 Copolymer of vinylidene fluoropropylene 10 Triallylcyanurate 1-2 Azo-bisisobutyronitrile 0.05-0.2 Triethylene glycol trinitrate 5-20
 3. A castable binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 46-58 1H, 1H, 5H-octafluoro-1-pentanoacrylate 21-23 Copolymer of vinylidene fluoride and perfluoropropylene 10 Triallylcyanurate 1-2 Azo-bisisobutyronitrile 0.05-0.1 Diethylene glycol dinitrate 10-20
 4. A castable binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 46-62 1H, 1H, 5H-octafluoro-1-pentanoacrylate 21-23 Copolymer of vinylidene fluoride and perfluoropropylene 10 Triallylcyanurate 1-2 Benzoyl peroxide 0.05- 0.1 1,4-butanediol dinitrate 5-20
 5. A castable binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 51-56 1H, 1H, 5H-octafluoro-1- pentanoacrylate 16-22 Copolymer of vinylidene fluoride and perfluoropropylene 10 Triallylcyanurate 1-2 Azo-bisisobutyronitrile 0.05- 0.2 Pentaerythritol trinitrate 10-15
 6. A castable binder composition comprising the following constituents: a fluorocarbon monomer selected from the group consisting of 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-1-heptanoacrylate, 1H, 1H, 5H-octafluoro-1-pentaenoacrylate and mixtures thereof; a vinyl monomer selected from the group consisting of acrylic acid, acrylonitrile, vinylacetate, dinitropropylacrylate, styrene and mixtures thereof; a plasticizer selected from the group consisting of triethylene glycol dinitrate, pentaerythritol trinitrate, trimethylol ethane trinitrate, diethylene glycol dinitrate, butanediol dinitrate, a copolymer of vinylidene fluoride and perfluoropropylene, bis(2-fluoro-2,2-dinitroethyl) formal and mixtures thereof; a cross-linking agent selected from the group consisting of triallylcyanurate and divinyl benzene; and a catalyst selected from the group consisting of azo-bisiso-butyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide.
 7. A castable binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 52-56 1H, 1H, 5H-octafluoro-1-pentanoacrylate 15-18 Copolymer of vinylidene fluoride and perfluoropropylene 10 Styrene 5 Triallylcyanurate 1-2 Benzoyl peroxide 0.01-0.2 Diethylene glycol dinitrate 10- 15
 8. The composition of claim 7 with trimethylol ethane trinitrate in lieu of diethylene glycol dinitrate.
 9. The composition of claim 7 with 1,4-butanediol dinitrate in lieu of diethylene glycol dinitrate.
 10. The composition of claim 7 with pentaerythritol trinitrate in lieu of diethylene glycol dinitrate.
 11. The composition of claim 7 with triethylene glycol dinitrate in lieu of diethylene glycol dinitrate.
 12. A fluorocarbon binder composition comprising the following constituents: a fluorocarbon monomer selected from the group consisting of 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-1-heptanoacrylate, 1H, 1H, 5H-octafluoro-1-pentanoacrylate and mixtures thereof; a cross-linking agent selected from the group consisting of triallylcyanurate and divinyl benzene; and a catalyst selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide, and methyl ethylketone peroxide.
 13. A fluorocarbon binder composition comprising the following constituents: 1H, 1H, 9H-hexadecafluoro-1-nonanomethacrylate 1H, 1H, 5H-octafluoro-1-pentanoacrylate Triallylcyanurate Azo-bisisobutyronitrile.
 14. A fluorocarbon binder composition comprising the following constituents: 1H, 1H, 5H-octafluoro-1-pentanoacrylate Triallylcyanurate Azo-bisisobutyronitrile.
 15. A fluorocarbon binder composition comprising the following constituents: Constituents Percent by weight Fluorocarbon monomer 95-99 Cross-linking agent 0.3-5 Catalyst 0.5-1 said fluorocarbon monomer selected from a group consisting of 1H, 1H, 9H-hexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-1-heptanoacrylate, 1H, 1H, 5H-octafluoro-1-pentanoacrylate, 1H, 1H, 9H-hexadecafluoro-1-nonanomethyacrylate; said cross-linking agent selected from a group consisting of triallylcyanurate and divinyl benzene; and said catalyst selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide.
 16. A binder composition comprising the following constituents: Constituents Percent by weight Fluorocarbon monomer 94-96 Vinyl monomer 1-5 Cross-linking agent 0.3- 4 Catalyst 0.1- 1 said fluorocarbon being a member selected from a group consisting of 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate, 1H, 1H, 9H-hexadecafluoro-1-nonanoacrylate, 1H, 1H, 7H-dodecafluoro-1-heptanoacrylate, 1H, 1H, 5H-octafluoro- 1-pentanoacrylate and mixtures thereof; said vinyl monomer being a member selected from a group consisting of acrylic acid, acrylonitrile, vinylacetate, dinitropropylacrylate and styrene; said cross-linking agent being a member selected from the group consisting of triallylcyanurate and divinyl benzene; and said catalyst being a member selected from the group consisting of azo-bisisobutyronitrile, benzoyl peroxide, dichlorobenzoyl peroxide and methylethylketone peroxide.
 17. A binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 65-85 1H, 1H, 5H-octafluoro-1-pentanoacrylate 14- 30 Acrylic acid 1-5 Triallylcyanurate 0.3-1 Azo-bisisobutyronitrile 0.1- 1
 18. A binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 65- 79 1H, 1H, 5H-octafluoro-1-pentanoacrylate 17- 30 Acrylonitrile 1.5- 5 Triallylcyanurate 0.3- 1 Azo-bisisobutyronitrile 0.1-0.5
 19. A binder composition comprising the following constituents: Constituents Percent by weight 1H, 1H, 9H-hexadecafluoro-1-monomethacrylate 53-60 1H, 1H, 5H-octafluoro-1-pentanoacrylate 20- 24 Dinitropropylacrylate 5- 20 Azo-bisisobutyronitrile 0.1- 0.3 Triallylcyanurate 0.3- 1 